Recycled resin composition

Abstract

The present invention relates to a resin composition comprising recycled resin, wherein the purpose of the present invention is to prevent problems such as gases or low molecular weight materials such as oligomers originating from the recycled resin accumulating and migrating to an injection-molded product or mold corrosion caused by the mold deposit in the process of injecting the resin composition, by using an appropriate content of antioxidant.

Description

Regenerated resin composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0162391, filed November 21, 2023, the entire disclosure of which is incorporated herein by reference.

[0003] [Technical Field]

[0004] The present invention relates to a regenerative resin composition.

[0005] Rapid advancements in advanced materials and devices are driving the development of ever-increasing new technologies and the continued advancement of diverse technological equipment. Consequently, consumption of electrical and electronic devices has increased, and the amount of waste generated is also steadily increasing. Plastics are widely used in electrical and electronic devices due to their low hazards and low cost. However, their low compressibility and high elasticity make them bulky during recycling, making recycling difficult.

[0006] Meanwhile, with growing global concern for the environment, regulations to curb carbon dioxide emissions are being strengthened. In particular, environmental pollution caused by the increased use of plastics has recently emerged as a serious problem. Therefore, an increasing number of countries are adopting producer responsibility recycling systems for plastics as part of the global circular economy trend. Furthermore, regulations at the manufacturing stage, such as mandating the use of recycled resins, are being strengthened, particularly in the United States. Plastic taxes and carbon border taxes are also being introduced. Consequently, recycling methods for waste plastics and the introduction of biomaterials are being explored in various ways. Accordingly, manufacturers are required to add a certain amount of recycled resin to the production of resin molded products, and eco-friendliness ratings are assigned based on the amount of recycled resin present.

[0007] However, since recycled resin is already a processed resin, it contains additives such as colorants, lubricants, and release agents, and its properties have already changed as it goes through a high-temperature processing process, so as the content of recycled resin increases, the physical properties inevitably deteriorate compared to the existing resin, and in particular, problems such as mold corrosion in the post-processing process of resin molded products or residual gas or low-molecular-weight substances such as oligomers appearing on the injection-molded product occur, making it difficult to actually commercialize it.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 0001) CN 110157131 A

[0011] The present invention provides a resin composition in which the generation of low molecular weight substances such as gases or oligomers derived from the recycled resin is reduced during the process of injecting the resin composition including the recycled resin.

[0012] (1) The present invention provides a resin composition comprising: a new graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; a new non-graft copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit; a regenerated resin comprising the conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; and an acid scavenger, wherein the acid scavenger is contained in an amount of 0.015 parts by weight or more and 0.55 parts by weight or less based on 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin.

[0013] (2) The present invention provides a resin composition in the above (1), wherein the acid neutralizing agent is an oxide or zeolite of a Group 2 metal element.

[0014] (3) The present invention provides a resin composition comprising 0.03 parts by weight or more and 0.5 parts by weight or less of the acid neutralizing agent relative to 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin in any one of the above (1) or (2).

[0015] (4) The present invention provides a resin composition in which, after continuously injecting the resin composition 500 times into a mold having a gas collection hole formed therein, the weight of the residue including residual gas or oligomers captured in the gas collection hole is 53.5 mg or less in any one of the above (1) to (3).

[0016] (5) The present invention provides a resin composition comprising 10 parts by weight or more and 60 parts by weight or less of the regenerated resin relative to 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin in any one of the above (1) to (4).

[0017] (6) The present invention provides a resin composition comprising 15 parts by weight or more and 50 parts by weight or less of the regenerated resin relative to 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin in any one of the above (1) to (5).

[0018] (7) The present invention provides a resin composition comprising 15 parts by weight or more and 40 parts by weight or less of the regenerated resin relative to 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin in any one of the above (1) to (6).

[0019] (8) The present invention provides a resin composition comprising 30 parts by weight or more and 75 parts by weight or less of the new non-graft copolymer, based on 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin, in any one of the above (1) to (7).

[0020] (9) The present invention provides a resin composition having an impact strength of 18 kg·cm / cm or more, measured according to the ASTM D256 method, for a sample having a thickness of 1 / 4 inch, in any one of the above (1) to (8).

[0021] In the case of a resin composition including a regenerated resin according to the present invention, the generation of low molecular weight substances such as gas or oligomers derived from the regenerated resin can be reduced during the process of injecting the resin composition.

[0022] Hereinafter, the present invention will be described in more detail to facilitate understanding. The terms and words used in this specification and claims should not be interpreted based on their conventional or dictionary meanings. Based on the principle that the inventor can appropriately define the concepts of terms to best explain his or her invention, they should be interpreted in a way that aligns with the technical spirit of the present invention.

[0023] In the present invention, the term 'monomer unit' may refer to a component, structure, or substance itself derived from a monomer, and as a specific example, may refer to a repeating unit formed within a polymer by a monomer introduced during polymerization of the polymer and participating in the polymerization reaction.

[0024] In the present invention, the 'weight average molecular weight' is generally measured by gel permeation chromatography (GPC). For example, after dissolving the sample to be measured in a THF (tetrahydrofuran) solution, the relative value to a standard sample (PS, standard polystyrene) can be measured through gel permeation chromatography (GPC).

[0025] The term 'composition' as used in the present invention includes a mixture of materials comprising the composition as well as reaction products and decomposition products formed from the materials of the composition.

[0026] In the present invention, the 'average particle diameter' may refer to the arithmetic mean particle diameter in the particle size distribution measured by dynamic light scattering, specifically, the scattering intensity average particle diameter. The average particle diameter of the conjugated diene polymer can be measured using the Nicomp 380 equipment (product name, manufacturer: PSS Nicomp).

[0027]

[0028] Resin composition

[0029] The present invention provides a resin composition.

[0030] A resin composition according to one embodiment of the present invention comprises: a new graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; a new non-graft copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit; a regenerated resin comprising the conjugated diene polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit; and an acid scavenger, wherein the acid scavenger is contained in an amount of 0.015 parts by weight or more and 0.55 parts by weight or less based on 100 parts by weight of the sum of the new graft copolymer, the new non-graft copolymer, and the regenerated resin.

[0031] The inventors of the present invention have discovered that, during the process of injecting a resin composition including a recycled resin, problems such as gas or low molecular weight substances such as oligomers (hereinafter, also referred to as "mold deposits") originating from the recycled resin accumulating and coming out on the injection-molded product, or mold corrosion occurring due to the mold deposits, can be solved by using an appropriate amount of an antioxidant, thereby completing the present invention.

[0032]

[0033] According to one embodiment of the present invention, the resin composition may be continuously injected 500 times into a mold having a gas collection hole formed therein, and the weight of the residue including the residual gas or oligomer captured in the gas collection hole may be 53.5 mg or less, and for specific examples, 50 mg or less, 49.5 mg or less, 49 mg or less, 48.5 mg or less, 48 ​​mg or less, 47.5 mg or less, 47 mg or less, 46.5 mg or less, 46 mg or less, 45.5 mg or less, or 45 mg or less. When the weight of the residue including the residual gas or oligomer captured in the gas collection hole satisfies the above range, mold corrosion may not occur.

[0034]

[0035] According to one embodiment of the present invention, the resin composition may have an impact strength of 17.5 kg·cm / cm or more, as measured according to the ASTM D256 method for a sample having a thickness of 1 / 4 inch, and for specific examples, may be 17.6 kg·cm / cm or more, 17.7 kg·cm / cm or more, 17.8 kg·cm / cm or more, 17.9 kg·cm / cm or more, or 18 kg·cm / cm or more. When the impact strength of the resin composition satisfies the above range, the resin composition including the recycled resin may satisfy the impact resistance requirement for use as a molded article.

[0036]

[0037] Hereinafter, each component of a resin composition according to one embodiment of the present invention will be described.

[0038]

[0039] 1. Regenerated resin

[0040] According to one embodiment of the present invention, recycled resin is a component included in a resin composition to obtain certification as an eco-friendly product. It is a recycled product obtained by processing and reusing used resin or resin waste. Specifically, the recycled resin may refer to resin waste collected, shredded, washed, separated, and sorted, then processed and reused for a specific purpose. The form of the recycled resin is not particularly limited.

[0041] According to one embodiment of the present invention, the recycled resin may be at least one selected from the group consisting of recycled polyethylene, recycled polypropylene, recycled polyester, recycled polystyrene, recycled polyamide, recycled polycarbonate, recycled diene-based graft polymer, and recycled vinyl-based non-graft polymer.

[0042] According to one embodiment of the present invention, the regenerated resin may include a conjugated diene monomer unit, a vinyl cyan monomer unit, and an aromatic vinyl monomer unit. The conjugated diene monomer unit may improve the impact resistance of the regenerated resin. The vinyl cyan monomer unit may improve the chemical resistance of the regenerated resin. In addition, the aromatic vinyl monomer unit may improve the processability of the regenerated resin.

[0043] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit included in the regenerated resin may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, and a specific example thereof may be 1,3-butadiene.

[0044] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the regenerated resin may be at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, styrene, p-fluoro styrene, p-chloro styrene, and p-bromo styrene, and a specific example thereof may be styrene.

[0045] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the regenerated resin may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0046]

[0047] According to one embodiment of the present invention, the regenerated resin has an Izod impact strength measured according to ASTM D256 of 7 kg·cm / cm or more and 30 kg·cm / cm or less, and as a specific example, it may be 7 kg·cm / cm or more and 25 kg·cm / cm or less, and as a more specific example, it may be 10 kg·cm / cm or more and 20 kg·cm / cm or less. If the above-described conditions are satisfied, a resin composition having minimum mechanical properties while obtaining a carbon reduction effect can be implemented.

[0048] According to one embodiment of the present invention, the regenerated resin has a flow index measured according to ASTM D1238 of 5 g / 10 min or more and 50 g / 10 min or less, specifically, 15 g / 10 min or more and 40 g / 10 min or less, and even more specifically, 25 g / 10 min or more and 35 g / 10 min or less. If the above conditions are satisfied, a resin composition having a carbon reduction effect and minimum mechanical properties can be realized.

[0049]

[0050] According to one embodiment of the present invention, the resin composition may contain the regenerated resin in an amount of 10 parts by weight or more and 60 parts by weight or less, based on 100 parts by weight of the contents of the regenerated resin, the new graft copolymer, and the new non-graft copolymer, and for specific examples, it may contain 12 parts by weight or more, 14 parts by weight or more, 16 parts by weight or more, 18 parts by weight or more, or 20 parts by weight or more, and further, it may contain 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less. When the above-described ranges are satisfied, the impact strength and flow index of the resin composition may be improved.

[0051]

[0052] 2. New graft copolymers

[0053] According to one embodiment of the present invention, the new graft copolymer is a graft copolymer that has never been used before and is a component that improves the impact resistance of a thermoplastic resin composition.

[0054] According to one embodiment of the present invention, the new graft copolymer may be a graft polymer including a conjugated diene polymer including a conjugated diene monomer unit as a rubber polymer and a shell including an aromatic vinyl monomer unit and a vinyl cyan monomer unit grafted onto the conjugated diene polymer. The shell may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit that are not grafted onto the conjugated diene polymer.

[0055]

[0056] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit included in the new graft copolymer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, and a specific example thereof may be 1,3-butadiene.

[0057] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the new graft copolymer may be at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, styrene, p-fluoro styrene, p-chloro styrene, and p-bromo styrene, and a specific example thereof may be styrene.

[0058] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the new graft copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0059]

[0060] According to one embodiment of the present invention, the content of the conjugated diene polymer included in the new graft copolymer may be 40 to 80 wt%, preferably 50 to 70 wt%. When the above-described conditions are satisfied, the impact resistance of the new graft polymer composition can be further improved.

[0061] According to one embodiment of the present invention, the content of the aromatic vinyl monomer unit included in the new graft copolymer may be 10 to 50 wt%, preferably 20 to 40 wt%. When the above-described conditions are satisfied, the processability of the new graft copolymer can be further improved.

[0062] According to one embodiment of the present invention, the content of vinyl cyan monomer units included in the new graft copolymer may be 1 to 30 wt%, preferably 5 to 25 wt%. When the above-described conditions are satisfied, the chemical resistance of the new graft polymer composition can be further improved.

[0063]

[0064] According to one embodiment of the present invention, the resin composition may comprise a single type of new graft copolymer or may comprise different types of new graft copolymers. For example, the resin composition may comprise new graft copolymers having different average particle diameters.

[0065]

[0066] According to one embodiment of the present invention, the resin composition may contain 15 parts by weight or more and 40 parts by weight or less of the new graft copolymer, based on 100 parts by weight of the content of the regenerated resin, the new graft copolymer, and the new non-graft copolymer, and for specific examples, it may contain 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, and further, it may contain 38 parts by weight or less, 36 parts by weight or less, 34 parts by weight or less, 32 parts by weight or less, or 30 parts by weight or less. When the above-described range is satisfied, the impact strength and flow index of the resin composition may be improved.

[0067]

[0068] 3. Novel non-graft copolymers

[0069] According to one embodiment of the present invention, the new non-graft copolymer is a non-graft copolymer that has never been used before and is a component that improves the tensile strength and processability of a resin composition.

[0070] According to one embodiment of the present invention, the new non-grafted copolymer is a non-grafted copolymer and may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit.

[0071] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the new non-graft copolymer may be at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, styrene, p-fluoro styrene, p-chloro styrene, and p-bromo styrene, and a specific example thereof may be styrene.

[0072] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the new non-graft copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0073]

[0074] According to one embodiment of the present invention, the content of the aromatic vinyl monomer unit included in the new graft copolymer may be 60 to 90 wt%, preferably 65 to 85 wt%. When the above-described conditions are satisfied, the processability of the new graft copolymer can be further improved.

[0075] According to one embodiment of the present invention, the content of vinyl cyanide monomer units included in the new non-graft copolymer may be 10 to 40 wt%, preferably 15 to 35 wt%. When the above-described conditions are satisfied, the chemical resistance of the diene-based graft polymer can be further improved.

[0076]

[0077] According to one embodiment of the present invention, the resin composition may contain 30 parts by weight or more and 75 parts by weight or less of the new non-graft copolymer, based on 100 parts by weight of the content of the regenerated resin, the new graft copolymer, and the new non-graft copolymer, and for specific examples, it may contain 32 parts by weight or more, 34 parts by weight or more, 36 parts by weight or more, 38 parts by weight or more, or 40 parts by weight or more, and further, it may contain 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, or 50 parts by weight or less. When the above-described range is satisfied, the impact strength and flow index of the resin composition may be improved.

[0078]

[0079] 4. Acid neutralizer

[0080] According to one embodiment of the present invention, an acid scavenger can play a role in reducing the generation of low molecular weight substances such as gases or oligomers derived from the regenerated resin when injecting a resin composition including the regenerated resin.

[0081]

[0082] According to one embodiment of the present invention, the low molecular weight substance such as a gas or oligomer derived from the regenerated resin may include, for example, moisture remaining when the resin composition is not sufficiently dried, monomers and oligomers remaining in the resin composition without being used in the polymerization reaction, gases generated from the resin composition due to thermal decomposition during the resin composition processing process, etc.

[0083]

[0084] According to one embodiment of the present invention, the acid neutralizing agent may be an oxide or zeolite of a Group 2 metal element (Be, Mg, Ca, Sr, Ba, Ra). As a specific example, the acid neutralizing agent may include magnesium oxide (MgO), zeolite, etc., and preferably, magnesium oxide.

[0085] According to one embodiment of the present invention, the acid neutralizing agent, specifically, the oxide of a Group 2 metal element and the zeolite, is expected to generate an electrical attraction between the Group 2 metal element or a metal substance such as Al contained in the oxide of the Group 2 metal element and the zeolite and the low molecular weight substance such as a gas or oligomer derived from the regenerated resin generated during injection of the resin composition. Accordingly, it is expected that, during injection of the resin composition including the acid neutralizing agent, the low molecular weight substance such as a gas or oligomer derived from the regenerated resin escapes from the resin composition due to the electrical attraction.

[0086]

[0087] According to one embodiment of the present invention, the resin composition may contain the acid neutralizer in an amount of 0.015 parts by weight or more and 0.55 parts by weight or less, based on 100 parts by weight of the content of the regenerated resin, the new graft copolymer, and the new non-graft copolymer, and for specific examples, it may contain the acid neutralizer in an amount of 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, or 0.1 parts by weight or more, and further, it may contain the acid neutralizer in an amount of 0.53 parts by weight or less, 0.51 parts by weight or less, 0.48 parts by weight or less, 0.46 parts by weight or less, 0.44 parts by weight or less, 0.42 parts by weight or less, or 0.4 parts by weight or less. If the acid neutralizer is included in amounts exceeding the above range, the impact strength of the resin composition may be reduced. Furthermore, if the acid neutralizer is included in amounts below the above range, the effect of reducing the generation of low-molecular-weight substances such as gases or oligomers derived from the regenerated resin may be reduced.

[0088]

[0089] 5. Other additives

[0090] According to one embodiment of the present invention, the resin composition may further include other additives. The additives may be at least one selected from the group consisting of a lubricant, an antioxidant, a light stabilizer, a hydrolysis stabilizer, a release agent, a pigment, an antistatic agent, a conductive agent, an electromagnetic shielding agent, a magnetizing agent, a mineral filler, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, an antifriction and wear-resistant agent, and a coupling agent.

[0091] The above additives can be used without limitation as long as they are used in the technical field of the present invention, and a person skilled in the art can select the additives included in the present invention according to the purpose.

[0092]

[0093] <Molded product>

[0094] The present invention provides a molded article comprising the resin composition. For example, the molded article can be applied to various industrial fields such as various electrical and electronic products and automobile parts. As a molding method, general molding methods such as extrusion, injection, and casting can be applied. For example, in injection molding, compared to a product that aims to provide a matte molded article by corroding the surface of the mold, the molded article according to the present invention does not require corroding the surface of the mold, and even without post-processing the molded article, it is possible to provide a molded article having a matte and uniform surface in the injection-molded state.

[0095]

[0096] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0097]

[0098] Examples and Comparative Examples

[0099] The materials used in the examples and comparative examples are as follows.

[0100]

[0101] (1) New graft copolymer A: ABS graft polymer comprising a butadiene rubber polymer having a particle size of 100 nm and a shell of styrene units and acrylonitrile units grafted onto the butadiene rubber polymer.

[0102]

[0103] (2) New graft copolymer B: ABS graft polymer including a butadiene rubber polymer having a particle size of 300 nm and a shell of styrene units and acrylonitrile units grafted onto the butadiene rubber polymer.

[0104]

[0105] (3) New non-graft copolymer: Styrene / acrylonitrile non-graft polymer containing 25 wt% of acrylonitrile units

[0106]

[0107] (4) Regenerated resin: A regenerated vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer (manufactured by Hanil Green Tech Resin Co., Ltd.) with an Izod impact strength (kg·cm / cm, 1 / 4``) of 15 kg·cm / cm and a melt flow index (g / 10 min) of 11 g / 10 min was used.

[0108]

[0109] (5) Acid neutralizer A: Magnesium oxide (MgO; manufactured by ICL, product name RA-150)

[0110]

[0111] (5) Acid neutralizer B: Zeolite (manufactured by Aekyung Materials Co., Ltd., product name APS-30)

[0112]

[0113] (6) Acid neutralizer C: Titanium oxide (TiO2; manufactured by Lomon, product name BLR-896)

[0114]

[0115] (7) Acid neutralizer D: Zinc oxide (ZnO; manufactured by Deoksan Pharmaceutical Co., Ltd., product name ZnO)

[0116]

[0117] A resin composition was prepared by mixing 0.1 part by weight of a stabilizer and 3 parts by weight of a lubricant with 100 parts by weight of a new graft copolymer, a new non-graft copolymer, a regenerated resin, and an acid neutralizer in the amounts described in Tables 1 and 2 below.

[0118]

[0119] Experimental example

[0120] The resin compositions manufactured in the above examples and comparative examples were put into an extrusion mixer (MAXX_Leistritz, product name: ZSE27) at a processing temperature of 220°C, extruded to obtain pellets, and then sufficiently dried. Then, they were injected at a temperature of 270°C using an injection molding machine (LG Chemical, product name: LGH-100N) to manufacture samples. The mold deposit and the properties of the resin compositions of the manufactured samples were measured using the following methods.

[0121]

[0122] * Mold deposit evaluation: In order to measure residual gas or low molecular weight substances such as oligomers generated during the injection molding process, a gas collection hole was designed in a mold manufactured for evaluation, and the resin compositions manufactured in the examples and comparative examples were continuously injected 500 times using the same method as described above, and the weight of the residue collected in the collection hole was measured.

[0123] Meanwhile, the mold manufactured for the above evaluation is specifically designed to have an injection specimen extraction section configured at the upper and lower portions of the center, and a gas collection hole installed at the center so that residue generated during the continuous injection process can enter the center hole. The gas collection hole has a diameter of 5 cm and a depth of 1.5 cm. In addition, the injection machine ejector pin area was sealed with a rubber O-ring to minimize gas collection errors.

[0124]

[0125] * Izod impact strength: Measured according to ASTM D256 for 1 / 4 inch thick samples. In the present invention, impact strength was evaluated as excellent when it was 18 kg·cm / cm or more.

[0126]

[0127] * Flow index: Measured at 220℃ / 10kg according to the evaluation method specified in ASTM D1238.

[0128]

[0129] Example 12345678 New graft copolymer A (parts by weight) 15151515-151515B (parts by weight) 151515153014815 New non-graft copolymer (parts by weight) 5050505050532750 Regenerated resin (parts by weight) 2020202020155020 Activator (parts by weight) 33333333 Stabilizer (parts by weight) 0.10.10.10.10.10.10.10.1 Acid neutralizer A (parts by weight) 0.030.10.250.50.250.250.25-B (parts by weight)-------0.25 Mold deposit (mg)53.34536.330.337.534.646.846.4Impact strength(1 / 4``)2221201925211920Melt index(g / 10 min)2523211725201523

[0130] Comparative Example 123456 New graft copolymer A (parts by weight) 151515151515B (parts by weight) 151515151515 New non-graft copolymer (parts by weight) 70505050505050 Regenerated resin (parts by weight) -2020202020 Activator (parts by weight) 333333 Stabilizer (parts by weight) 0.10.10.10.10.10.1 Acid neutralizer (parts by weight) A (parts by weight) -- 0.60.015--B (parts by weight)------C (parts by weight)----0.25-D (parts by weight)-----0.25 Mold deposit (mg)53.858.529.156.955.355.9Impact strength(1 / 4``)192216222021Melt index(g / 10 min)282515252222

[0131] Referring to Tables 1 and 2, in the case of Examples 1 to 8, which included 0.015 to 0.55 parts by weight of the acid neutralizer relative to 100 parts by weight of the total of the new graft copolymer, the new non-graft copolymer, and the regenerated resin, it was confirmed that the mold deposit value was reduced while satisfying excellent impact strength and melt index compared to Comparative Example 2, which included the regenerated resin but did not include the acid neutralizer.

[0132]

[0133] In addition, it was confirmed that the resin compositions of Examples 1 to 8 had mold deposit values ​​similar to or lower than those of Comparative Example 1, which did not include recycled resin.

[0134]

[0135] In the case of Comparative Example 3, which contains more than 0.55 parts by weight of acid neutralizer, it was confirmed that it did not satisfy excellent impact strength compared to Examples 1 to 7.

[0136]

[0137] In the case of Comparative Example 4 containing less than 0.15 parts by weight of acid neutralizer, it was confirmed that the mold deposit value was not reduced compared to Examples 1 to 7.

[0138]

[0139] In the case of Comparative Example 5, which uses titanium oxide as an acid neutralizer, it was confirmed that the mold deposit value was not reduced compared to Examples 1 to 7, which use oxides of Group 2 metal elements or zeolites as acid neutralizers.

[0140]

[0141] In the case of Comparative Example 6, which uses zinc oxide as an acid neutralizer, it was confirmed that the mold deposit value was not reduced compared to Examples 1 to 7, which use oxides of Group 2 metal elements or zeolites as acid neutralizers.

Claims

1. A novel graft copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer unit and a vinyl cyan monomer unit; A novel non-grafted copolymer comprising an aromatic vinyl monomer unit and a vinyl cyan monomer unit; A regenerated resin comprising a conjugated diene polymer, an aromatic vinyl monomer unit and a vinyl cyan monomer unit; and Contains an acid scavenger, A resin composition comprising 0.015 parts by weight or more and 0.55 parts by weight or less of the acid neutralizing agent relative to 100 parts by weight of the new graft copolymer, the new non-graft copolymer, and the regenerated resin.

2. In paragraph 1, A resin composition wherein the acid neutralizing agent is an oxide of a Group 2 metal element or a zeolite.

3. In paragraph 1, For 100 parts by weight of the new graft copolymer, the new non-graft copolymer and the regenerated resin, A resin composition comprising 0.03 part by weight or more and 0.5 part by weight or less of the acid neutralizing agent.

4. In paragraph 1, A resin composition, wherein the weight of a residue including residual gas or oligomer trapped in the gas trapping hole is 53.5 mg or less after the resin composition is continuously injected 500 times into a mold having gas trapping holes formed therein.

5. In paragraph 1, For 100 parts by weight of the new graft copolymer, the new non-graft copolymer and the regenerated resin, A resin composition comprising 10 parts by weight or more and 60 parts by weight or less of the above-mentioned regenerated resin.

6. In paragraph 1, For 100 parts by weight of the new graft copolymer, the new non-graft copolymer and the regenerated resin, A resin composition comprising 15 parts by weight or more and 50 parts by weight or less of the above-mentioned regenerated resin.

7. In paragraph 1, For 100 parts by weight of the new graft copolymer, the new non-graft copolymer and the regenerated resin, A resin composition comprising 15 parts by weight or more and 40 parts by weight or less of the above-mentioned regenerated resin.

8. In paragraph 1, For 100 parts by weight of the new graft copolymer, the new non-graft copolymer and the regenerated resin, A resin composition comprising 30 parts by weight or more and 75 parts by weight or less of the above-mentioned new non-graft copolymer.

9. In paragraph 1, A resin composition having an impact strength of 18 kg·cm / cm or more as measured according to the ASTM D256 method for a sample having a thickness of 1 / 4 inch.